Process for preparing wetting agents



Patented Sept. 24, 1935 UNITED STATES PATENT orrics WalthenSchrauth,Berlin-Dahlem, Germany, as-

signor, by mesne assignments, to Unichem Ohemilralien Handels A.-G.,Zurich, Switzerland, a corporation of Switzerland No Drawing.

Application January 24, 1934,

Serial No. 708,075. In Germany January 30,

The present invention has for an object the production of washing-,cleansing-, wetting-out and emulsifying agents by conjoint sulfonationof fat like substances and aromatic or hydroaromatic hydrocarbons ormixed aromatic-hydroaromatic hydrocarbons respectively. 1

As everybody knows, the sulfonates of aromatic hydrocarbons andparticularly of naphthalene and of tetrahydronaphthalene, possess theproperty of converting substances insoluble in water into aqueoussolutions (hydrotropic properties). They are therefore not merely appied as admixtures to soaps of all kinds, but also as diluents forsoap-like substances such as are found 18 in the sulfates and sulfonatesof waxes fats, oils and especially of higher molecular fatty alcoholsand the like. Now, as a'rule, the conditions under which the sulfonatingprocess'le'ads to the production of sulfonates of aromatic hydrocar- 20bons are different from those under which an exhaustive suifonation, offor example the higher molecular fatty alcohols. is obtained. While insulfonating the latter one employs the lowest possible temperatures, theproduction of arcmatic sulfonic acids occurs as a rule at temperaturesof more than 100 C. Therefore it could not be expected without ado, thate. g. higher molecular alcohols might be conjointly sulfonated witharomatic hydrocarbons in such a manner that sulfates and sulfonates ofhigher molecular alcohols are obtained simultaneously with thesulfonates of aromatic hydrocarbons.

Now it has been found that materials of both groups can beconjointlysulfonated at low temperatures and in such a manner that eventhe aromatic hydrocarbons, which otherwise can be sulfonated only athigher temperatures, produce sulfonic acids even if the sulfonation isperformed at the lowest possible temperatures. It is also possible toemploy chlor sulfonic acid andsimilar sulfonating agents. One employsadvantageously chloro sulfonic acid in a proportion that ex,- ceeds byabout 10 to 20% the theoretically necessary proportion, the degreeofpurity being considered when determinating the respective, proportion.The aromatic hydrocarbon which at the beginning is still unsulfonated,acts as a solvent and insures even at very low temperatures a perfectsulfonation of the reaction mixture. The sulfonation, under theaforesaid condltions, is performed with quite surprising completeness sothat there is no need of any separate treatment of the singlecomponents. In only a single operation one obtains a mixture of sul- 55fonates similar to that which otherwise results 24 Claims. (01. as-1) bya mechanical mixing, conjoint grinding and the like of the singlecomponents; thus one saves the cost of the machines which would benecessary for the latter operations.

Compared with the well-known method of sul- 5 fonation of highermolecular alcohols in the presence of solvents which makes possible asulfonation at low temperatures the procedure of this invention isdistinguished not only by making it possibletosulfonate the appliedhydrocar- 1o bons at low temperatures but also by the simulsulfonatehigher molecular fatty or wax alcohols. 20

their esters and ethers, fatty acids, their esters with monoorpolyhydric alcohols, particularly glycerides, and furthermore waxes,fat-like substances and the like, but the alcohols or fatty acidsrespectively on which the said compounds 25 are based, should contain noless than 8 carbon atoms in the molecule. Among the alcohols to bec'onsideredthere may be mentioned first of all the-dodeyh, myristyl-,cetyl-, octadecyland the oleyl alcohol; among the fatty acids thebleic30 and ricinolic acid are particularly recommendable. The hydrocarbonssuitable for the'performing of the present procedure must have a lowpointofsolidiflcation and-they must themselves be sulfonable, thus tosecure a thorough 35 sulfonation even at low temperatures. Thesulfonates made of them areto be fit for converting substances insolublein-water into aqueous solutions.

The products obtained according to the pres- 40 ent method distinguishthemselves by an extraordinary stability ahd are superior to thepreparations obtained by mixing the single components. The degree ofsulfonation is considerably higher than that obtained by the separatesulfonation of the single components. They are fast toboiling in hardwater of (German hardness degreeiand-form solutions which are clear evenat very low temperatures. Their fastness 50 to acids is excellent. Owingto the low reaction temperatures which are applied, the reaction of thesulfonating agents is very mild and, therefore, the thus obtainedproducts are of a very light colour.

Example 1 1400 g. of oleyl alcohol of the iodine number and of acongealing-point of +2 are mixed with 500 g. of tetrahydronaphthalene.Into this mixture 1120 g. of chlorosulfonic acid are gradually stirredin the course of about 5 hours at a temperature of -5 to +5 underconstant cooling. By the neutralizing with a diluted solution of causticsoda one obtains about 4500 g. of a reaction product containingapproximately 30% of fat. The clarification point of 2% solutions is atabout 20.

Example 2 To a mixture consisting of 420 parts by weight of sperm oiland 260 parts by weight of tetrahydrophenanthrene (or weight parts ofcymol respectively), one adds gradually under stirring 280 parts byweight of chlorosulfonic acid at a temperature of -3 to +5 C. takingcare for a good cooling and then one continues to stir for three hours.The further treatment is carried out as per Example 1. The thus obtainedreaction product suits well for the production of emulsifying andwetting-baths.

Example 3 1500 g. of dioleylether of theiodine number 92 are mixed with500 g. of tetrahydronaphthalene and cooled down to about 0 C. Into thismass 1050 g. of chlorosulfonic acid are gradually dropped in the courseof about 4-5 hours while continuing the constant cooling and under a reular stirring. The reaction being terminated one neutralizes with adiluted solution of caustic soda and the thus obtained product showsexcellent capillary-active properties. It is also allowed to substituteother ethers for the dioleylether. particularly mixed ones such aslauryl-mono-glycolether, cetyl-mono-glycerineether and the like.

Example 4 1000 g. of oleic acid of a iodine number of 85 are mixed with400 g. of tetrahydromethylnaphthalene, whereupon the mixture is cooleddown to a temperature lying between 5 and +5 C. Into this mixture, whichis kept at the said temperature, one gradually drops 700 g. ofchlorosulfonic acid. The reaction product obtained after terminating thereaction and after neutralization is. advantageously applied forwashingand cleansing baths.

The term "sulfonation" as found in the claims is used in the broad senseto include both true sulfonation and sulfation.

The terms "sulfona "sulfonation" and the like are used in the broadsense to define the formation of sulfuric acid esters as well as theformation of true sulfonic acid, except where it is clear that the truesulfonation is intended.

What I claim is:

1. As a product of manufacture the composition of sulfonated sperm oilwith tetrahydrophenanthrene sulfonic acid, applicable as wetting-out-,washing-, cleansingand emulsifying agent.

2. 'As a. product of manufacture the composition of" sulfonated dioleylether with tetrahydronaphthalene sulfonic acid, applicable aswettingout-, washing-, cleansingand emulsifying agent.

3. As a. product of manufacture the composition of sulfonated oleic acidwith tetrabydromethylnaphthalene sulfonic acid, applicable aswetting-out-, washing-, cleansingand emulsifying agent.

ucts between both components.

4. The manufacture of washing, cleansing, wetting-out and emulsifyingagents characterized by the conjoint sulfonation of an aliphaticcompound selected from the group consisting of the primary aliphaticalcohols having 8 or more 5 carbon atoms in the molecule, the ethers ofthese alcohols with the same or other primary aliphatic alcohols, theesters of these alcohols with primary aliphatic carboxylic acids,primary aliphatic carboxylic acids having 8 or more car- 10 bon atoms inthe molecule and the esters of. these acids with primary monoandpoly-hydric aliphatic alcohols, and of an aromatic hydrocarbon withoutthe formation of condensation prod- 5. The manufacture of washing,cleansing, wetting-out and emulsifying agents characterized by theconjoint sulfonation of a primary aliphatic alcohol having 8 or morecarbon atoms in the molecule and of an aromatic hydrocarbon go withoutthe formation of condensation products between both components.

6. The manufacture of washing,v cleansing, wetting-out and emulsifyingagents character ized by the conjoint sulfonation of primary alig5phatic alcohol having 12 to 18 carbon atoms in the molecule and of anaromatic hydrocarbon at a temperature of the order of 5 to +5 C. withoutthe formation of condensation products between both components. 30

7. The manufacture of washing, cleansing, wetting-out and emulsifyingagents characterized by the conjoint sulfonation of primary aliphaticunsaturated alcohol having 12 to 18 carbon atoms in the molecule and ofan aromatic 35 hydrocarbon at a temperature'of the order of 5 to +5 C.without the formation of condensation products between both components.

8. The manufacture of washing, cleansing, wetting-out and emulsifyingagents character- 40 ized by the conjoint sulfonation of oleyl alcoholand of an aromatic hydrocarbon without the formation of condensationproducts between both components.

9. The manufacture of washing, cleansing, 45 wetting-out and emulsifyingagents characterized by the conjoint sulfonation of an ether of primaryaliphatic alcohols, at least one of which alcohols has 8 or more carbonatoms in the molecule and of an aromatic hydrocarbon with- 50 out theformation of condensation products between both components.

10. The manufacture of washing, cleansing, wetting-out and emulsifyingagents characterized by the conjoint sulfonation of ethers of pri 5 maryaliphatic alcohols both of which have 8 or more carbon atoms in themolecule and of an aromatic hydrocarbon without the formation ofcondensation products between both components.

11. The manufacture of washing, cleansing, wetting-out and emulsifyingagents characterized by the conioint sulfonation of di-oleyl ether andof an aromatic hydrocarbon without the formation of condensationproducts between both components.

12. The manufacture of washing, cleansing, wetting-out and emulsifyingagents characterized by the conjoint sulfonation of an ester of aprimary aliphatic alcohol and a primary all-- 70 phatic acid at leastone of which components has 8 or more carbon atoms in the moleculewithout the formation of condensation products between both components.

13. The manufacture of washing, cleansing, 75

wetting-out and emulsifying agents characterized by the conjointsulfonation of esters of primary aliphatic acid having 8 or more carbonatoms in the molecule with primary aliphatic alcohol and of an aromatichydrocarbon without the formation of condensation products between bothcomponents.

14. The manufacture of washing, cleansing, wetting-out and emulsifyingagents characterized by the conjoint sulfonation of esters of primaryaliphatic alcohol having 8 or more carbon atoms in the molecule withprimary aliphatic acid and of an aromatic hydrocarbon without theformation of condensation products between both components.

15. The manufacture of washing, cleansing, wetting-out and emulsifyingagents characterized by the conjoint sulfonation of esters of primaryaliphatic alcohol having 8 or more carbon atoms in the molecule withprimary aliphatic acid having 8 or more carbon atoms in the molecule andof an aromatic hydrocarbon without the formation of condensationproducts between both components.

16. The manufacture of washing, cleansing, wetting-out and emulsifyingagents characterized by the conjoint sulfonation of an unsatu rated waxester and of an aromatic hydrocar- -bon without the formation ofcondensation products between both components.

17. The manufacture of washing, cleansing, wetting-out and emulsifyingagents characterized by the conjoint sulfonation of sperm oil and of anaromatic hydrocarbon without the formation of condensation productsbetween both components.

18. The manufacture of washing, cleansing, wetting-out and emulsifyingagents characterized by the conjoint sulfonation of an aliphaticcompound selected from the group consisting of the primary aliphaticalcohols having 8 or more carbon atoms in the molecule, the ethers-ofthese alcohols with the same or other primary aliphatic alcohols, theesters of these alcohols with primary aliphatic carboxylic acids,primary aliphatic carboxylic acids having 8 or more carbon atoms in themolecule and the esters of these acids with primary monoand poly-hydricaliphatic alcohols, and of hydrocarbons of the group consisting ofnaphthalene, tetrahydronaphthalene, tetra hydro phenanthrene,-tetrahydromethyl naphthalene and cymol at low temperatures without the formationof condensation products between both components.

19. The manufacture of washing, cleansing, wetting-out and emulsifyingagents characterized by the conjoint sulfonation of an aliphaticcompound selected from the group consisting of the primary aliphaticalcohols having 8 or more carbon atoms in the molecule, the ethers ofthese alcohols with the same or other primary aliphatic alcohols, theesters of these alcohols with primary aliphaticcarboxylic acids, primaryaliphatic carboxylic acids having 8 or more carbon atoms in the moleculeand the esters of these acids with primary monoand poly-hydric aliphaticalcohols and of aromatic hydrocarbons of the naphthalene series at atemperature of the order of 5 to +5 C. without the formation ofcondensation products between the compm nents.

20. The manufacture of washing, cleansing, wetting-out and emulsifyingagents characterized by the conjoint sulfonation of an aliphaticcompound selected from the group consisting of the primary aliphaticalcohols having 8 or more carbon atoms in the molecule, the ethorsofthese a'cohols with the same or other primary aliphatic alcohols, theesters of these alcohols with primary 5 aliphatic carboxylic acids,primary aliphatic carboxyhc acids having 8 or more carbon atoms in themolecule and the esters of these acids with primary monoand poly-hydricaliphatic alcohols and of hydronaphthalene hydrocarbons 1 without theformation of condensation products between both components.

21. The manufacture of washing, cleansing, wetting-out and emulsifyingagents character-, ized by the conjoint sulfonation of an aliphatic 15compound seiected from the group consisting of the primary aliphaticalcohols having 8 or more carbon atoms in the molecule, the ethers ofthese alcohols with the same or other primary aliphatic alcohols, theesters of these alcohols with pri- 20 mary aliphatic carboxylic acids,primary aliphatic carboxylic acids having 8 or more carbon atoms in themolecule and the esters of these acids with primary monoand poly-hydricaliphatic alcohols and of aromatic hydrocarbons capable of 25 beingsulfonated to form emulsifying agents with out the formation ofcondensation products between both components.

22. The manufacture of washing, cleansing, wetting-out and emulsifyingagents character- 30 ized by the conjoint sulfonation ofan aliphaticcompound selected from the group consisting of the primary aliphaticalcohols having 8 or more carbon atoms in the molecule, the ethers ofthese alcohols with the same or other primary aliphatic 35 alcohols, theesters of these alcohols with primary aliphatic carboxylic acids,primary aliphatic carboxylic acids having 8 or more carbon atoms in themolecule and the esters of these acids with primary monoand poly-hydrlcaliphatic alco- 40 hols and of tetrahydronaphthalene without theformation of condensation products between both components.

23. The manufacture of washing, cleansing, wetting-out and emulsifyingagents character- 45 ized by the conjoint sulfonation of an aliphaticcompound selected from the group consisting of the primary aliphaticalcohols having 8 or more carbon atoms in the molecule, the ethers ofthese alcohols with the same or other primary aliphatic 60 alcohols, theesters of these alcohols with primary aliphatic carboxylic acids,primary aliphatic carboxylic acids having 8 or more carbon atoms in themolecule and the esters of these acids with primary monoand poly-hydricaliphatic alco- 55 hols and of tetrahydro phenanthrene without theformation of condensation products between both components.

24. The manufacture of washing, cleansing, wetting-out and emulsifyingagents character- 60 ized by the conjoint sulfonation of an aliphaticcompound selected from the group consisting of the primary aliphaticalcohols having 8 or more carbon atoms in the molecule, the ethers ofthese alcohols with the same or other pri mary aliphatic alcohols, theesters of these aicohols with primary aliphatic carboxylic acids,primary aliphatic carboxylic acids having 8 or more carbon atoms in themolecule and the esters of these acids with primary monoand poly- 70hydric aliphatic alcohols and of tetrahydro methyl naphthalene withoutthe formation of condensation products between both components.

WALTHER SCI-IRAU'HI,

